Graphene composite and method of producing the same

ABSTRACT

Provided is a graphite-based carbon material useful as a graphene precursor, from which graphene is easily exfoliated when the graphite-based carbon material is useful as a precursor and from which a highly-concentrated graphene dispersion can easily be obtained. The graphite-based carbon material is a graphite-based carbon material useful as a graphene precursor wherein a Rate (3R) based on an X-ray diffraction method, which is defined by following Equation 1 is 31% or more:
 
Rate (3 R )= P 3/( P 3+ P 4)×100  Equation 1
 
wherein
         P3 is a peak intensity of a (101) plane of the rhombohedral graphite layer (3R) based on the X-ray diffraction method, and   P4 is a peak intensity of a (101) plane of the hexagonal graphite layer (2H) based on the X-ray diffraction method.

CROSS REFERENCE TO RELATED APPLICATION

This application is a divisional of co-pending U.S. patent applicationSer. No. 14/651,630, filed Jun. 11, 2015, which is entirely incorporatedherein by reference.

TECHNICAL FIELD

The present invention relates to a graphene composite using a grapheneprecursor and a method of producing the same.

BACKGROUND ART

In recent years, addition of various nanomaterials has been studied forpurposes of downsizing and weight saving in various fields. Inparticular, for problems of environments or resources, carbon materialssuch as graphene, CNT (carbon nanotube) and fullerene have attractedattention as nonmetal nanomaterials.

For example, although carbon black has been used as a conductiveassistant for lithium-ion batteries and the like, carbon nanofiber VGCF(registered trademark) manufactured by Showa Denko K.K., etc. have beenstudied in recent years to further secure conductivity (PatentLiterature 1).

Among them, graphene is superior to other carbon materials in aspect ofmass productivity, handleability, etc., as well as performance, andexpectations have been placed on graphene in various fields.

In order to obtain high-quality graphene which, for example, has fewergraphite layers, a method in which weak ultrasonic waves are applied tonatural graphite in a solvent (NMP) for a long time (7-10 hours), largeagglomerates which deposit on the bottom are then removed, and thesupernatant is then centrifuged to concentrate it, thereby obtaining agraphene dispersion in which 20% or more of flakes of a single layer,40% or more of flakes of double or triple layers, and less than 40% offlakes of 10 layers or more of a graphite material are dispersed atabout 0.5 g/L, has been considered (Patent Literature 2).

CITATION LIST Patent Literature

-   PTL 1: JP-A-2013-77475 (Paragraph 0023)-   PTL 2: WO 2014/064432 (lines 4-9 on page 19)

Non Patent Literature

-   NPL 1: Structural Change of Graphite Caused by Grinding; authors:    Michio INAGAKI, Hisae MUGISHIMA, and Kenji HOSOKAWA; Feb. 1, 1973    (Received)-   NPL 2: Changes of Probabilities P1, PABA, PABC with Heat Treatment    of Carbons; authors: Tokiti NODA, Masaaki IWATSUKI, and Michio    INAGAKI; Sep. 16, 1966 (Received)-   NPL 3: Spectroscopic and X-ray diffraction studies on fluid    deposited rhombohedral graphite from the Eastern Ghats Mobile Belt,    India; G. Parthasarathy, Current Science, Vol. 90, No. 7, 10 Apr.    2006-   NPL 4: Classification of solid carbon materials and their structural    characteristics; Nagoya Institute of Technology; Shinji KAWASAKI

SUMMARY OF INVENTION Technical Problem

However, even when the graphite material (20% or more of flakes of asingle layer, 40% or more of flakes of double or triple layers, and lessthan 40% of flakes of 10 layers or more) obtained by the methoddisclosed in Patent Literature 2 was mixed into a solvent, the amount ofgraphene dispersed in the solvent was small, and only a dilute graphenedispersion could be obtained. Additionally, although it is consideredthat a supernatant is collected and concentrated, it takes a longtimefor treatments to repeat the steps of collecting and concentrating thesupernatant, and there is a problem of inferior production efficiency ofa graphene dispersion. As disclosed in Patent Literature 2, even bysubjecting natural graphite to an ultrasonic treatment for a long time,only weak parts of the surface are exfoliated, other large parts do notcontribute to the exfoliation, and it is considered as a problem thatthe amount of exfoliated graphene is small.

The invention was completed focusing on such problem points, and agraphite-based carbon material, from which graphene is easily exfoliatedby carrying out predetermined treatments to natural graphite, and whichmakes it possible to disperse graphene at a high concentration or to ahigh degree is called a graphene precursor. Then, an object of theinvention is to provide a graphite-based carbon material useful as sucha graphene precursor, as well as a method of producing the same.

Solution to Problem

In order to solve the above-mentioned problems, a graphene composite ofthe present invention comprises at least a graphene is partiallyexfoliated from the graphite-based carbon material and dispersed in abase material,

the graphite-based carbon material having a rhombohedral graphite layer(3R) and a hexagonal graphite layer (2H), wherein a Rate (3R) of therhombohedral graphite layer (3R) and the hexagonal graphite layer (2H),based on an X-ray diffraction method, which is defined by followingEquation 1, is 31% or more:Rate (3R)=P3/(P3+P4)×100  (Equation 1)wherein

-   -   P3 is a peak intensity of a (101) plane of the rhombohedral        graphite layer (3R) based on the X-ray diffraction method, and    -   P4 is a peak intensity of a (101) plane of the hexagonal        graphite layer (2H) based on the X-ray diffraction method,

the graphene being a crystal of a mean size of 100 nm or more and formedin a flake-like or sheet-like shape having 10 layers or less.

Accordingly, the graphene is highly dispersed in the graphene composite,whereby properties of the graphene composite are improved.

Further, the graphene composite is used as a resin molded article. As aresult, the strength of the resin molded article is improved bydispersing graphene therein.

Further, the base material is a resin and a compatibilizer is dispersedin the base material. As a result, the graphene is easily exfoliated bythe action of the compatibilizer and the strength of the resin moldedarticle is further improved.

Further, the graphene composite is used as conductive ink. As a result,conductivity of the conductive ink is improved by dispersing graphenetherein.

Further, the base material is at least one of a solvent and aconductivity-imparting agent. As a result, the conductive ink isexcellent in conductivity.

Further, a method of producing a graphene composite comprises a step ofmixing at least a graphite-based carbon material in a base material,wherein graphene is partially exfoliated from the graphite-based carbonmaterial and dispersed in the base material,

the graphite-based carbon material having a rhombohedral graphite layer(3R) and a hexagonal graphite layer (2H), wherein a Rate (3R) of therhombohedral graphite layer (3R) and the hexagonal graphite layer (2H),based on an X-ray diffraction method, which is defined by followingEquation 1, is 31% or more:Rate (3R)=P3/(P3+P4)×100  (Equation 1)wherein

-   -   P3 is a peak intensity of a (101) plane of the rhombohedral        graphite layer (3R) based on the X-ray diffraction method, and    -   P4 is a peak intensity of a (101) plane of the hexagonal        graphite layer (2H) based on the X-ray diffraction method,

the graphene being a crystal of a mean size of 100 nm or more and formedin a flake-like or sheet-like shape having 10 layers or less.

Accordingly, the graphene is highly dispersed in the graphene composite,whereby properties of the graphene composite are improved.

Further, the base material is a resin, the mixing step involves kneadingwhile applying shearing force, and the graphene composite is a resinmolded article. As a result, the graphene is easily exfoliated in thegraphene composite and the graphene composite having improved strengthcan be obtained.

Further, a compatibilizer is added and kneaded in the base material inthe mixing step. As a result, the graphene is easily exfoliated by theaction of the compatibilizer and the resin molded article excellent instrength can be obtained.

Further the graphene composite is conductive ink. As a result, theconductive ink having improved conductivity can be obtained bydispersing graphene therein.

Further, the base material is at least one of a solvent and aconductivity-imparting agent. As a result, the conductive ink havingimproved conductivity can be easily obtained.

Further, the graphite-based carbon material useful as a grapheneprecursor of the invention is characterized by having a rhombohedralgraphite layer (3R) and a hexagonal graphite layer (2H), wherein a Rate(3R) of the rhombohedral graphite layer (3R) and the hexagonal graphitelayer (2H), based on an X-ray diffraction method, which is defined byfollowing Equation 1 is 31% or more:Rate (3R)=P3/(P3+P4)×100  Equation 1wherein

-   -   P3 is a peak intensity of a (101) plane of the rhombohedral        graphite layer (3R) based on the X-ray diffraction method, and    -   P4 is a peak intensity of a (101) plane of the hexagonal        graphite layer (2H) based on the X-ray diffraction method.

According to the features, since a large amount of the rhombohedralgraphite layer (3R) from which a layer is easily exfoliated is includedtherein, a graphite-based carbon material useful as a grapheneprecursor, from which graphene is easily exfoliated when thegraphite-based carbon material is useful as a precursor, and which makesit possible to disperse graphene at a high concentration or to a highdegree can be obtained.

The graphite-based carbon material useful as a graphene precursor of theinvention is characterized in that the Rate (3R) is 40% or more.

According to the feature, as long as the Rate (3R) is 40% or more, agraphite-based carbon material useful as a graphene precursor from whichgraphene is more easily exfoliated, compared with cases where the Rate(3R) is 31% or more and less than 40%, can easily be obtained.

The graphite-based carbon material useful as a graphene precursor of theinvention is characterized in that the Rate (3R) is 50% or more.

According to the feature, as long as the Rate (3R) is 50% or more, agraphite-based carbon material useful as a graphene precursor from whichgraphene is more easily exfoliated, compared with cases where the Rate(3R) is 40% or more and less than 50%, can easily be obtained.

The graphite-based carbon material useful as a graphene precursor of theinvention is characterized in that an intensity ratio P1/P2 of thehexagonal graphite layer (2H) based on the X-ray diffraction method is0.01 or more, wherein

P1 is a peak intensity of a (100) plane of the hexagonal graphite layer(2H) based on the X-ray diffraction method, and

P2 is a peak intensity of a (002) plane of the hexagonal graphite layer(2H) based on the X-ray diffraction method.

According to the feature, when the intensity ratio P1/P2 of thehexagonal graphite layer (2H) is made 0.01 or more, the orientationdisorder of crystal structure of carbon material will be higher,graphene is easily exfoliated, and the graphite-based carbon materialcan be made to more effectively function as the precursor.

The above-described graphite-based carbon material useful as a grapheneprecursor is characterized in that the graphite-based carbon material isproduced by carrying out a radiowave-force-based treatment and aphysical-force-based treatment in a vacuum or in the air.

According to the feature, by combining a treatment based on a radiowaveforce by microwaves, millimeter waves, plasma, electromagnetic inductionheating (IH), magnetic fields or the like, and a treatment based on aphysical force by a ball mill, jet mill, centrifugal force,supercriticality or the like, to a natural graphite material in a vacuumor in the air, a graphite-based carbon material including morerhombohedral graphite layers (3R) is obtained. In addition, since thetreatments are carried out in a vacuum or in the air, aftertreatmentsare simple.

A method of producing a graphite-based carbon material useful as agraphene precursor of the invention is characterized by including:carrying out a radiowave-force-based treatment and aphysical-force-based treatment to a natural graphite material in avacuum or in the air.

According to the feature, by combining a treatment based on a radiowaveforce by microwaves, millimeter waves, plasma, electromagnetic inductionheating (IH), magnetic fields or the like, and a treatment based on aphysical force by a ball mill, a jet mill, a centrifugal force,supercriticality or the like, a graphite-based carbon material useful asa graphene precursor, which more easily separates into graphene,compared with use of either one of the treatments, can be obtained in ashort time.

A method of producing a graphite-based carbon material useful as agraphene precursor of the invention is characterized in that theabove-described natural graphite material has at least a hexagonalgraphite layer (2H), and an intensity ratio P1/P2 of the hexagonalgraphite layer (2H) based on the X-ray diffraction method is less than0.01, wherein

P1 is a peak intensity of a (100) plane of the hexagonal graphite layer(2H) based on the X-ray diffraction method, and

P2 is a peak intensity of a (002) plane of the hexagonal graphite layer(2H) based on the X-ray diffraction method.

According to the features, the carbon material can be produced fromeasily-available natural graphite of which the orientation disorder ofcrystal structure of carbon material is lower and general.

The graphite-based carbon material of the invention is characterized byhaving a rhombohedral graphite layer (3R) and a hexagonal graphite layer(2H), wherein a Rate (3R) of the rhombohedral graphite layer (3R) andthe hexagonal graphite layer (2H), based on an X-ray diffraction method,which is defined by following Equation 1 is 31% or more:Rate (3R)=P3/(P3+P4)×100  Equation 1wherein

P3 is a peak intensity of a (101) plane of the rhombohedral graphitelayer (3R) based on the X-ray diffraction method, and

P4 is a peak intensity of a (101) plane of the hexagonal graphite layer(2H) based on the X-ray diffraction method.

According to the features, the graphite-based carbon material thatcontains a large amount of the rhombohedral graphite layer (3R) which iseasily exfoliated to layers can be obtained.

Furthermore other aspects are following.

A graphene dispersion is characterized in that the graphene dispersionis obtained by carrying out a radiowave-force-based treatment and aphysical-force-based treatment to the above-described graphite-basedcarbon material useful as a graphene precursor in a liquid.

According to the feature, in a liquid such as a solvent, heat acts onthe graphite-based carbon material due to the radiowave force bymicrowaves, millimeter waves, plasma, electromagnetic induction heating(IH), magnetic fields or the like, and a physical force further actsthereon by a ball mill, a jet mill, a centrifugal force,supercriticality or the like. Therefore, by combining theradiowave-force-based treatment and the physical-force-based treatment,a large amount of graphene is easily exfoliated in a short time, agraphite-based carbon material from which graphene is not exfoliated andwhich remains in the liquid as a solvent is less, and graphene is highlydispersed therein. Consequently, a large amount of graphene can bedispersed in the liquid such as a solvent, and a concentrated graphenedispersion is obtained.

The graphene dispersion is characterized by containing at least 0.01 ormore parts by weight of graphene.

According to this feature, when at least 0.01 or more parts by weight ofgraphene is present, the graphene has high dispersibility, andtherefore, functions caused by dispersions of the graphene cansufficiently be exerted.

A graphene composite is characterized in that the graphene composite isobtained by mixing the above-described graphite-based carbon materialuseful as a graphene precursor or the above-described graphenedispersion with a composite base material, followed by kneading themwhile applying a shearing force to them.

According to the feature, the above-described graphite-based carbonmaterial or the above-described graphene dispersion and the compositebase material are kneaded while applying a shearing force to them, andtherefore, graphene is easily exfoliated therefrom, and exfoliatedgraphene is highly dispersed therein. Consequently, a graphenecomposite, which can disperse a large amount of graphene in a compositebase material such as monomers, polymers, other carbon materials,ceramics, wood, cements, or metals, is obtained.

The graphene composite is characterized in that a compatibilizer is usedin kneading the graphene precursor or the graphene dispersion with thecomposite base material.

According to the feature, due to effects of the compatibilizer, grapheneis more easily exfoliated.

The graphene dispersion is characterized in that, when 0.1 part byweight of the above-described graphite-based carbon material useful as agraphene precursor is mixed with N-methylpyrrolidone (NMP), and anultrasonic wave with an output of 100 W and with a frequency of 20 kHzis applied to the resulting mixture for 3 hours to thereby dispersegraphene, 50% or more of an amount of graphene each having 10 layers orless are exposed relative to a total amount of all graphene and grapheneprecursors.

According to the feature, by only carrying out the above-describedtreatments to 0.1 part by weight of the graphite-based carbon materialuseful as a graphene precursor, a graphene dispersion in which grapheneis dispersed at a high concentration or to a high degree, such that theamount of graphene each having 10 layers or less is 50% or more relativeto a total amount of all graphene and graphene precursors, can beobtained.

A graphite-based carbon material useful as a graphene precursor ischaracterized in that the graphite-based carbon material used withkneading a composite base material.

According to the feature, a shearing force is applied to thegraphite-based carbon material with kneading them, and therefore,graphene is easily exfoliated therefrom, and exfoliated graphene ishighly dispersed therein. Consequently, a graphene composite, which candisperse a large amount of graphene in a composite base material such asmonomers, polymers, other carbon materials, ceramics, wood, cements, ormetals, is obtained.

The graphene in a composite base material is characterized in that thecomposite base material is a resin.

According to the feature, a resin molded article having a high degreedispersed graphene can be obtained. For example, a resin molded articlehaving an excellent elastic modulus can be obtained.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a figure which shows a crystal structure of graphite, whereFIG. 1(a) refers to a crystal structure of hexagonal crystals, and FIG.1(b) refers to a crystal structure of rhombohedral crystals.

FIG. 2 is a diagram which shows an X-ray diffraction profile of generalnatural graphite.

FIG. 3 is a diagram which illustrates a production apparatus A using ajet mill and plasma of Example 1.

FIGS. 4(a) and 4 (b) are figures which illustrate a production apparatusB using a ball mill and magnetron of Example 1, where FIG. 4 (a) is adiagram which illustrates a pulverizing state, and FIG. 4 (b) is adiagram which illustrates a state where graphite-based carbon materials(precursors) are collected.

FIG. 5 is a diagram which shows an X-ray diffraction profile of agraphite-based carbon material of Sample 5 produced by the productionapparatus B according to Example 1.

FIG. 6 is a diagram which shows an X-ray diffraction profile of agraphite-based carbon material of Sample 6 produced by the productionapparatus A according to Example 1.

FIG. 7 is a diagram which shows an X-ray diffraction profile of agraphite-based carbon material of Sample 1 indicating a comparativeexample.

FIG. 8 is a diagram which shows a dispersion-producing apparatus whichproduces a dispersion using a graphite-based carbon material as aprecursor.

FIG. 9 is a diagram which shows dispersing states of dispersionsproduced by using graphite-based carbon materials of Sample 1 indicatinga comparative example, and Sample 5 produced by the production apparatusB of Example 1.

FIGS. 10(a) and 10(b) are TEM images of a graphite-based carbon material(graphene) dispersed in a dispersion.

FIGS. 11(a) and 11(b) are figures which show distribution states of agraphite-based carbon material dispersed in a dispersion which wasproduced using a graphite-based carbon material (precursor) of Sample 5,where FIG. 11(a) is a diagram which shows an average size distribution,while FIG. 11 (b) is a diagram which shows a distribution of the numberof layers.

FIGS. 12(a) and 12(b) are figures which show a distribution state of agraphite-based carbon material dispersed in a dispersion which wasproduced using a graphite-based carbon material of Sample 1 indicatingthe comparative example, where FIG. 12(a) is a diagram showing anaverage size distribution, and FIG. 12(b) is a diagram showing adistribution of the number of layers.

FIG. 13 is a diagram which shows distributions of the number of layersof graphite-based carbon materials each dispersed in dispersions thatwere produced using Samples 1 to 7 as precursors.

FIG. 14 is a diagram which shows proportions of graphene having 10layers or less to a content of rhombohedral crystals dispersed in adispersion.

FIGS. 15(a) and 15(b) are figures which show a distribution state ofgraphite when varying conditions for producing a dispersion using agraphite-based carbon material (precursor) of Sample 5 according toExample 2, where FIG. 15 (a) is a diagram showing a distribution in acase where an ultrasonic treatment and a microwave treatment werecombined, while FIG. 15 (b) is a diagram showing a distribution of thenumber of layers in a case where an ultrasonic treatment was conducted.

FIG. 16 is a diagram which shows a resistance value when agraphite-based carbon material of Example 3 was dispersed in aconductive ink.

FIG. 17 is a diagram which shows a tensile strength when agraphite-based carbon material of Example 4 was kneaded with a resin.

FIG. 18 is a diagram which shows a tensile strength when agraphite-based carbon material of Example 5 was kneaded with a resin.

FIGS. 19(a) and 19(b) are diagrams which show dispersing states ofgraphite-based carbon materials of dispersions for describing dispersingstates of Example 5 supplementary, where FIG. 19(a) is a dispersingstate of sample 12, and FIG. 19(b) is a dispersing state of sample 2.

DESCRIPTION OF EMBODIMENTS

The invention focuses on a crystal structure of graphite, and, at first,matters relating to the crystal structure will be explained. It has beenknown that natural graphite is classified into three types of crystalstructures, namely hexagonal crystals, rhombohedral crystals anddisordered crystals, depending on an overlapping manner of layers. Asshown in FIGS. 1(a) and 1 (b), hexagonal crystals have a crystalstructure in which layers are arranged in the order of ABABAB . . . ,while rhombohedral crystals have a crystal structure in which layers arearranged in the order of ABCABCABC . . . .

In natural graphite, there are almost no rhombohedral crystals in astage where natural graphite is excavated. However, about 14% ofrhombohedral crystals exist in general natural graphite-based carbonmaterials because pulverization or the like is carried out in apurification stage. In addition, it has been known that a proportion ofrhombohedral crystals converges on about 30% even when pulverization iscarried out during purification for a long time (Non-Patent Literatures1 and 2).

Moreover, a method in which graphite is expanded by heating, rather thanwith physical forces such as pulverization, thereby flaking thegraphite. However, even when graphite is treated with a heat of 1600 K(about 1,300° C.), a proportion of rhombohedral crystals is about 25%(Non-Patent Literature 3). Furthermore, the proportion is up to about30% even when heat of an extremely high temperature of 3000° C. isapplied thereto (Non-Patent Literature 2).

Thus, although it is possible to increase a proportion of rhombohedralcrystals by treating natural graphite with physical forces or heat, theupper limit is about 30%.

Hexagonal crystals (2H), which are included in natural graphite at ahigh level, are very stable, and an interlayer van der Waals' forcebetween their graphene layers is shown by Equation 3 (Patent Literature2). By applying an energy exceeding this force, graphene is exfoliated.An energy required for the exfoliation is inversely proportional to thecube of the thickness. Therefore, in a thick state where numerous layersare overlapped, graphene is exfoliated by a weak physical force such asby very feeble ultrasonic waves. However, in a case where graphene isexfoliated from somewhat thin graphite, a very large energy is required.In other words, even if graphite is treated for a long time, only weakparts of the surface are exfoliated, and large parts remain notexfoliated.Fvdw=H·A/(6n·t ³)  Equation 3

Fvdw: Van der Waals' force

H: Hamaker constant

A: Surface area of graphite or graphene

t: Thickness of graphite or graphene

The present inventors succeeded in increasing a proportion ofrhombohedral crystals (3R), which had been increased to only about 30%by treatments of pulverization or heating to an extremely hightemperature, to 30% or more by carrying out predetermined treatments, asshown below, to natural graphite. The following findings were obtainedas results of experiments and studies. That is, when a content ofrhombohedral crystals (3R) in a graphite-based carbon material ishigher, particularly when the content is 31% or more, there is atendency that graphene is easily exfoliated by use of such agraphite-based carbon material as a precursor, thereby easily obtaininga highly concentrated and dispersed graphene dispersion or the like. Forthe reason, it is considered that, when a shear force or the like isapplied to rhombohedral crystals (3R), a deformation occurs betweenlayers, i.e. a deformation in the entire structure of the graphitebecomes large, and graphene is easily exfoliated independently of thevan der Waals' force. Accordingly, in the invention, a graphite-basedcarbon material, from which graphene is easily exfoliated by carryingout predetermined treatments to natural graphite, and which makes itpossible to disperse graphene at a high concentration or to a highdegree, is called a graphene precursor. Hereinafter, a method ofproducing a graphene precursor showing predetermined treatments, acrystal structure of the graphene precursor, and a graphene dispersionusing the graphene precursor will be described in that order in examplesbelow.

Here, in the specification, a graphene refers to a flake-like orsheet-like graphene which is a crystal of a mean size of 100 nm or morebut which is not a fine crystal of a mean size of several nanometers totens of nanometers, and which has 10 layers or less.

Additionally, since graphene is a crystal with a mean size of 100 nm ormore, when artificial graphite and carbon black, which are amorphous(microcrystal) carbon materials other than natural graphite, are eventreated, graphene cannot be obtained (Non-Patent Literature 4).

Further, in the specification, a graphene composite means a compositewhich is produced by using the graphite-based carbon material useful asa graphene precursor according to the invention, i.e. a graphite-basedcarbon material having a Rate (3R) of 31% or more (e.g. Samples 2-7 ofExample 1, samples 2, 21, of Example 5 described below).

Hereinafter, examples for carrying out the graphene composite using thegraphene precursor and the method of producing the same, according tothe present invention, will be described.

Example 1 As to Production of a Graphite-Based Carbon Material Useful asa Graphene Precursor

A method for obtaining a graphite-based carbon material useful as agraphene precursor by a production apparatus A using a jet mill andplasma shown in FIG. 3 will be explained. As an example, the productionapparatus A refers to a case in which plasma is applied for theradiowave-force-based treatment and in which the jet mill is used forthe physical-force-based treatment.

In FIG. 3, the symbol 1 refers to a particle of 5 mm or less of anatural graphite material (flaky graphite ACB-50 manufactured by NipponGraphite Industries, ltd.); the symbol 2 refers to a hopper which storesthe natural graphite material 1; the symbol 3 refers to a Venturi nozzlewhich discharges the natural graphite material 1 from the hopper 2; thesymbol 4 refers to a jet mill which jets the air which has been pumpedfrom a compressor 5, while being divided into eight places, to therebyallow the natural graphite material to collide against the inside of achamber by a jet blast; and the symbol 7 refers to a plasma generatorwhich sprays a gas 9, such as oxygen, argon, nitrogen or hydrogen,through a nozzle 8 from a tank 6 and which applies a voltage to a coil11, wound around the outer periphery of the nozzle 8, from ahigh-voltage power supply 10, thereby generating plasma inside thechamber of the jet mill 4, and the plasma generator is provided in eachof four places inside the chamber. The symbol 13 refers to a pipe whichconnects the jet mill 4 and a dust collector 14 to one another; thesymbol 14 refers to a dust collector; the symbol 15 refers to acollection container; the symbol 16 refers to a graphite-based carbonmaterial (graphene precursor); and the symbol 17 refers to a blower.

Next, the production method will be explained.

Conditions for the jet mill and plasma are as follows.

The conditions for the jet mill are as follows.

Pressure: 0.5 MPa

Air volume: 2.8 m³/min

Nozzle inner Diameter: 12 mm

Flow rate: about 410 m/s

The conditions for plasma are as follows.

Output: 15 W

Voltage: 8 kV

Gas species: Ar (purity 99.999 vol %)

Gas flow rate: 5 L/min

It is considered that the natural graphite materials 1, which have beencharged into the chamber of the jet mill 4 from the Venturi nozzle 3,are accelerated to the sonic velocity or higher inside the chamber, andare pulverized by impact between the natural graphite materials 1 or byimpact of them against the wall, and that, simultaneously, the plasma 12discharges an electric current or excites the natural graphite materials1, acts directly on atoms (electrons), and increases deformations ofcrystals, thereby promoting the pulverization. When the natural graphitematerials 1 turn into fine particles of a certain particle diameter(about 1 to 10 μm), their mass is reduced, the centrifugal force isweakened, and, consequently, the natural graphite materials 1 are pumpedout from the pipe 13 which is connected to the center of the chamber.

A gas including graphite-based carbon materials (graphene precursors),which have been flowed from the pipe 13 into a cylindrical container ofthe chamber of the dust collector 14, forms a spiral flow, and drops thegraphite-based carbon materials 16, which collide with the internal wallof the container, to a collection container 15 below, while an ascendingair current generates in the center of the chamber due to a taperedcontainer part of the downside of the chamber, and the gas is emittedfrom the blower 17 (so-called cyclone effects). According to theproduction apparatus A in this example, about 800 g of a grapheneprecursor from 1 kg of the raw materials, i.e. natural graphitematerials 1, is used. The graphite-based carbon material (grapheneprecursors) 16 was obtained (recovery efficiency: about 80%).

Next, based on the production apparatus B using a ball mill andmicrowaves shown in FIGS. 4(a) and 4(b), a method for obtaining agraphite-based carbon material useful as a graphene precursor will bedescribed. The apparatus B refers to, as an example, a case wheremicrowaves are applied as the radiowave-force-based treatment and wherea ball mill is used for the physical-force-based treatment.

In FIGS. 4 (a) and 4(b), the symbol 20 refers to the ball mill; thesymbol 21 refers to a microwave generator (magnetron); the symbol 22refers to a wave guide; the symbol 23 refers to a microwave inlet; thesymbol 24 refers to a media; the symbol 25 refers to particles of 5 mmor less of a natural graphite material (flaky graphite ACB-50manufactured by Nippon Graphite Industries, ltd.); the symbol 26 refersto a collection container; the symbol 27 refers to a filter; and thesymbol 28 refers to graphite-based carbon material (grapheneprecursors).

Next, the production method will be explained. Conditions for the ballmill and the microwave generator are as follows.

The conditions for the ball mill are as follows.

Rotational speed: 30 rpm

Media size: φ5 mm

Media species: zirconia balls

Pulverization time: 3 hours

The conditions for the microwave generator (magnetron) are as follows.

Output: 300 W

Frequency: 2.45 GHz

Irradiation method: Intermittent

1 kg of natural graphite carbon raw materials 25 and 800 g of media 24are charged into the chamber of the ball mill 20, the chamber is closed,and the mixture is treated at a rotational speed of 30 rpm for 3 hours.During the treatment, microwaves are irradiated intermittently (for 20seconds every 10 minutes) to the chamber. It is considered that themicrowave irradiation acts directly on atoms (electrons) of the rawmaterials, thus increasing deformations of the crystals. After thetreatment, media 24 are removed by the filter 27, and thus, powder ofabout 10 μm of graphite-based carbon materials (precursors) 28 can becollected in the collection container 26.

<As to an X-Ray Diffraction Profile of Graphite-Based Carbon Materials(Graphene Precursors)>

With reference to FIGS. 5 to 7, X-ray diffraction profiles and crystalstructures will be described with respect to graphite-based naturalmaterials (Samples 6 and 5) produced by the production apparatuses A andB, and the powder of about 10 μm of graphite-based natural materials(Sample 1: a comparative example) obtained by using only the ball millof the production apparatus B.

The measurement conditions for the X-ray diffraction apparatus are asfollows.

Source: Cu Kα ray

Scanning speed: 20°/min

Tube voltage: 40 kV

Tube current: 30 mA

According to the X-ray diffraction method(horizontal-sample-mounting-model multi-purpose X-ray diffractometerUltima IV manufactured by Rigaku Corporation), each sample shows peakintensities P1, P2, P3 and P4 in the planes (100), (002) and (101) ofhexagonal crystals 2H and in the plane (101) of rhombohedral crystals3R. Therefore, these peak intensities will be explained.

Here, the measurements of X-ray diffraction profile have been used theso-called standardized values at home and abroad in recent years. Thishorizontal-sample-mounting-model multi-purpose X-ray diffractometerUltima IV manufactured by Rigaku Corporation is an apparatus which canmeasure X-ray diffraction profile in accordance with JIS R 7651:2007“Measurement of lattice parameters and crystallite sizes of carbonmaterials”. In addition, Rate (3R) is the ratio of the diffractionintensity obtained by the Rate (3R)=P3/(P3+P4)×100, even if the value ofthe diffraction intensity is changed, the value of Rate (3R) is notchanges. Means that the ratio of the diffraction intensity isstandardized, it is commonly used to avoid performing the identificationof the absolute value substance and its value does not depend onmeasurement devices.

As shown in FIG. 5 and Table 1, Sample 5 produced by the productionapparatus B, which applies a treatment with a ball mill and a microwavetreatment, had high rates of peak intensities P3 and P1, and a Rate (3R)defined by Equation 1 showing a rate of P3 to a sum of P3 and P4 was46%. Additionally, the intensity ratio P1/P2 was 0.012.Rate (3R)=P3/(P3+P4)×100  Equation 1wherein

P1 is a peak intensity of a (100) plane of the hexagonal graphite layer(2H) based on the X-ray diffraction method,

P2 is a peak intensity of a (002) plane of the hexagonal graphite layer(2H) based on the X-ray diffraction method,

P3 is a peak intensity of a (101) plane of the rhombohedral graphitelayer (3R) based on the X-ray diffraction method, and

P4 is a peak intensity of a (101) plane of the hexagonal graphite layer(2H) based on the X-ray diffraction method.

TABLE 1 Peak intensities [counts · deg] (2θ [°]) Hexagonal crystals 2H(100) 162 [P1] (42.33) Hexagonal crystals 2H (002) 13157 [P2] (26.50)Rhombohedral crystals 3R (101) 396 [P3] (43.34) Hexagonal crystals 2H(101) 466 [P4] (44.57)

In the same manner, as shown in FIG. 6 and Table 2, Sample 6 produced bythe production apparatus A, which applies a treatment based on the jetmill and a treatment based on plasma, had high rates of peak intensitiesP3 and P1, and the Rate (3R) was 51%. In addition, the intensity ratioP1/P2 was 0.014.

TABLE 2 Peak intensities [counts · deg] (2θ [°]) Hexagonal crystals 2H(100) 66 [P1] (42.43) Hexagonal crystals 2H (002) 4,675 [P2] (26.49)Rhombohedral crystals 3R (101) 170 [P3] (43.37) Hexagonal crystals 2H(101) 162 [P4] (44.63)

Furthermore, as shown in FIG. 7 and Table 3, Sample 1 indicating acomparative example produced with only the ball mill had a small rate ofa peak intensity P3, compared with Samples 5 and 6, and the Rate (3R)was 23%. In addition, the intensity ratio P1/P2 was 0.008.

TABLE 3 Peak intensities [counts · deg] (2θ [°]) Hexagonal crystals 2H(100) 120 [P1] (42.4) Hexagonal crystals 2H (002) 15,000 [P2] (26.5)Rhombohedral crystals 3R (101) 50 [P3] (43.3) Hexagonal crystals 2H(101) 160 [P4] (44.5)

Thus, Sample 5 produced by the production apparatus B of Example 1, andSample 6 produced by the production apparatus A of Example 1 had Rates(3R) of 46% and 51%, respectively, and it was shown that their Rates(3R) were 40% or more, or 50% or more, compared with the naturalgraphite shown in FIG. 2 and Sample 1 indicating a comparative example.

Next, graphene dispersions were produced using the above-producedgraphene precursors, and their easiness in exfoliation of graphene wasevaluated.

<As to Graphene Dispersions>

A method for producing a graphene dispersion will be explained withreference to FIG. 8. FIG. 8 shows, as an example, a case where anultrasonic treatment and a microwave treatment are combined in a liquidwhen a graphene dispersion is produced.

(1) 0.2 g of a graphite-based carbon material useful as a grapheneprecursor and 200 ml of N-methylpyrrolidone (NMP) which serves asdispersing medium are charged to a beaker 40.

(2) The beaker 40 is put into a chamber 42 of a microwave generator 43,and an ultrasonic trembler 44A of an ultrasonic horn 44 is inserted intodispersing medium 41 from the upper direction.

(3) The ultrasonic horn 44 is activated, and ultrasonic waves of 20 kHz(100 W) are continuously applied thereto for 3 hours.

(4) While the above ultrasonic horn 44 is actuated, the microwavegenerator 43 is activated to apply microwaves of 2.45 GHz (300 W)intermittently (irradiation for 10 seconds every 5 minutes) thereto.

FIG. 9 refers to appearances of graphene dispersions produced in theabove-described way when 24 hours had passed.

Although a portion of the graphene dispersion 30 using Sample 5 producedby the production apparatus B was deposited, a product entirely showinga black color was observed. For this, it is considered that a largeportion of the graphite-based carbon materials used as grapheneprecursors are dispersed in a state where graphene is exfoliated fromthem.

In the dispersion 31 using Sample 1 indicating a comparative example,most of the graphite-based carbon materials were deposited, and it wasconfirmed that a portion thereof floated as a supernatant. From thefacts, it is considered that graphene was exfoliated from a smallportion thereof and that they floated as the supernatant.

Furthermore, the graphene dispersion produced in the above-described waywas diluted to an observable concentration, was coated onto a samplestage (TEM grid), and the grid was dried. Thus, the size and the numberof layers of graphene was observed in the captured image of atransmission electron microscope (TEM), as shown in FIGS. 10(a) and10(b). In addition, the grid coated with the diluted supernatant wasused for Sample 1. For example, in the case of FIGS. 10(a) and 10(b),the size corresponds to a maximum length L of a flake 33, which was 600nm, based on FIG. 10(a). As for the number of layers, the end face ofthe flake 33 was observed in FIG. 10(b), and overlapping graphene layerswere counted, thereby calculating the number of layers as 6 layers (aportion indicated by the symbol 34). In this way, the size and thenumber of layers were measured with respect to each flake (“N” indicatesthe number of flakes), and the numbers of graphene layers and the sizesshown in FIGS. 11 and 12 were obtained.

With reference to FIG. 11 (a), a particle size distribution(distribution of sizes) of thin flakes included in the graphenedispersion of Sample 5 (Rate (R3) of 46%) produced by the productionapparatus B of Example 1 was a distribution having a peak of 0.5 μm. Inaddition, in FIG. 11 (b), as to the number of layers, a distributionwhich had a peak in 3 layers and in which graphene having 10 layers orless were 68% was observed.

With reference to FIGS. 12(a) and 12(b), a particle size distribution(distribution of sizes) of thin flakes included in the dispersion ofSample 1 (Rate (R3) of 23%) of the comparative example was adistribution having a peak of 0.9 μm. In addition, as for the number oflayers, a distribution in which those having 30 layers or more occupiedthe greater portion and in which graphene having 10 layers or less were10% was observed.

From the results, it was revealed that, when the product of Sample 5produced by the production apparatus B was used as a graphene precursor,a highly-concentrated graphene dispersion which contains plenty ofgraphene of 10 layers or less and which has excellent dispersibility ofgraphene can be obtained.

Next, with reference to FIG. 13, a relation between the Rate (3R) of thegraphene precursor and the number of layers in the graphene dispersionwill be described. Samples 1, 5 and 6 in FIG. 13 are those describedabove. Samples 2, 3 and 4 were produced by the production apparatus 13which carried out a treatment based on a ball mill and a microwavetreatment, and were graphene dispersions produced using grapheneprecursors which had been produced by making the irradiating time ofmicrowaves shorter than that for Sample 5. In addition, Sample 7 wasproduced by the production apparatus A which carried out a treatmentbased on a jet mill and a plasma treatment, and was a graphenedispersion produced by using a graphene precursor which had beenproduced by applying plasma of a higher output than that for Sample 6.

From FIG. 13, as to Samples 2 and 3 showing Rates (3R) of 31% and 38%,respectively, the distributions of the number of layers have peaks ataround 13 as the number of layers; that is, the shapes of thedistributions are close to that of a normal distribution (dispersionsusing Samples 2 and 3). As to Samples 4 to 7 showing Rates (3R) of 40%or more, the distributions of the number of layers have peaks at severalas the number of layers (thin graphene); that is, the shapes of thedistributions are those of a so-called lognormal distribution. On theother hand, as to Sample 1 having a Rate (3R) of 23%, the distributionthereof has a peak at 30 or more as the number of layers (a dispersionusing Sample 1). That is, it is understood as follows: there is atendency that, in cases where the Rate (3R) reaches 31% or more, theshapes of the layer number distributions differ from those for caseswhere the Rate (3R) is less than 31%; and further, in cases where theRate (3R) reaches 40% or more, the shapes of the layer numberdistributions clearly differ from those for cases where the Rate (3R) isless than 40%. In addition, it can be understood that, as to proportionsof graphene of 10 layers or less, the Rate (3R) of the dispersion usingSample 3 is 38%, while the Rate (3R) of the dispersion using Sample 4 is42%, and that, when the Rate (3R) reaches 40% or more, a proportion ofgraphene of 10 layers or less rapidly increases.

From these facts, it can be considered that graphene of 10 layers orless are easily exfoliated in cases where the Rate (3R) is 31% or more,and that, as the Rate (3R) increases to 40%, 50% and 60%, graphene of 10layers or less are more easily exfoliated. In addition, focusing on theintensity ratio P1/P2, Samples 2 to 7 show values within a comparativelynarrow range of 0.012 to 0.016, and any of them are preferable becausethey exceed 0.01 where it is considered that graphene is easilyexfoliated since crystal structures will be deformed.

Furthermore, results obtained by comparing Rates (3R) and proportions ofgraphene of 10 layers or less included therein are shown in FIG. 14.With reference to FIG. 14, it was revealed that, when the Rate (3R)reached 25% or more, around 31%, graphene of 10 layers or less startedto increase (showing an ever-increasing slope). Further, it was revealedthat, around 40%, graphene of 10 layers or less rapidly increased (as toproportions of graphene of 10 layers or less, whereas the Rate (3R) ofthe dispersion using Sample 3 was 38%, the Rate (3R) of the dispersionusing Sample 4 was 62%, and the proportion of graphene of 10 layers orless rapidly increased by 24% as the Rate (3R) increased by 4%), andthat a percentage of graphene of 10 layers or less against the totalgraphene was 50% or more. In addition, the points of black squares inFIG. 14 each correspond to different samples, and above-describedSamples 1 to 7 and other samples are included therein.

From the facts, when a sample showing a Rate (3R) of 31% or more is usedas a graphene precursor to produce a graphene dispersion, the proportionof distributed graphene of 10 layers or less starts increasing; further,when a sample showing a Rate (3R) of 40% or more is used as a grapheneprecursor to produce a graphene dispersion, 50% or more of graphene of10 layers or less are produced. In other words, a graphene dispersion inwhich graphene is highly concentrated and highly dispersed can beobtained. Furthermore, because almost no graphite-based carbon materials(precursors) included in the dispersion deposit as described above, aconcentrated graphene dispersion can easily be obtained. According tothis method, even a graphene dispersion whose graphene concentrationexceeded 10% can be produced without concentrating it. Particularly, theRate (3R) is preferably 40% or more from a view point that theproportion of dispersed graphene of 10 layers or less sharply increasesto 50% or more.

The above description clarifies the following: when the Rate (3R) is 31%or more, preferably 40% or more, and further preferably 50% or more,separation into graphene of 10 layers or less and thin graphite-basedcarbon materials of around 10 layers occurs in a greater proportion inmany cases; and in the case where these graphite-based carbon materialsare used as graphene precursors, a highly-concentrated graphenedispersion that has excellent dispersibility of graphene can beobtained. Still further, Example 5 to be described below clarifies that,in the case where the Rate (3R) is 31% or more, graphite-based carbonmaterials are useful as a graphene precursor.

Furthermore, an upper limit for the Rate (3R) is considered that theupper limit is not particularly defined. However, it is preferable thatthe upper limit is defined such that the intensity ratio P1/P2simultaneously satisfies 0.01 or more, because graphene precursors areeasily exfoliated when a dispersion or the like is produced. Inaddition, in cases of production methods using production apparatuses Aand B, the upper limit is about 70%, from a viewpoint that graphene iseasily produced. Also, a method combining a treatment based on the jetmill of the production apparatus A and a plasma treatment is morepreferable, because a graphene precursor having a higher Rate (3R) caneasily be obtained. Additionally, the Rate (3R) as long as it reaches31% or more by combining the physical-force-based treatment and theradiowave-force-based treatment.

Example 2

In Example 1, a case where the ultrasonic treatment and the microwavetreatment were combined for obtaining a graphene dispersion isexplained. In Example 2, only an ultrasonic treatment was carried outwhile a microwave treatment was not carried out, and other conditionswere the same as those for Example 1.

FIG. 15 (b) shows a distribution of a number of layers with respect to agraphene dispersion which was obtained by carrying out an ultrasonictreatment using the graphene precursor of Sample 5 (Rate (3R)=46%)produced by the production apparatus B. In addition, FIG. 15 (a) is thesame as the distribution shown in FIG. 11 (b) of Sample 5 produced bythe production apparatus B of Example 1.

As a result, although the tendency of the distribution of the number oflayers was almost similar, a proportion of graphene of 10 layers or lesswas 64%, and was slightly decreased, compared with 68% of Example 1.From the fact, it was revealed that it was more effective tosimultaneously carry out two of the treatments based on a physical forceand a radiowave force for producing a graphene dispersion.

Example 3

In Example 3, an example used for a conductive ink will be described.

Sample 1 (Rate (3R)=23%), Sample 3 (Rate (3R)=38%), Sample 5 (Rate(3R)=46%) and Sample 6 (Rate (3R)=51%) of Example 1 were used asgraphene precursors in mixture solution of water and an alcohol of thecarbon number of 3 or less, which severed as a conductivity-impartingagent, at concentrations adopted for conductive inks, thus producingINK1, INK3, INK5 and INK6, and their resistance values were compared.Based on the results, as the Rates (3R) became higher, the resistancevalues were lower.

Example 4

In Example 4, an example in which a graphene precursor was kneaded witha resin will be explained.

When a resin sheet, in which graphene was dispersed, was produced, thetensile strength was very superior although glass fibers were addedthereto. Therefore, a factor for this was studied, and, consequently, afinding that a compatibilizer added simultaneously with the glass fiberscontributed to formation of graphene from the precursor could beobtained. Therefore, products obtained by mixing dispersing agents and acompatibilizer into a resin were studied.

1 wt % of Sample 5 (Rate (3R)=46%) of Example 1 was added as a precursordirectly to LLDPE (polyethylene), and the mixture was kneaded whileapplying shear (a shearing force) thereto with a kneader, two-shaftkneader (extruder) or the like.

It has been publicly known that, when a graphite-based carbon materialsturned into graphene, being highly dispersed in a resin, the tensilestrength increases. Therefore, by measuring a tensile strength of theresin, degrees of exfoliating into graphene and dispersion canrelatively be estimated. The tensile strength was measured with an exacttabletop general-purpose testing machine (AUTOGRAPH AGS-J) manufacturedby Shimadzu Corporation under a condition of test speed of 500 mm/min.

In addition, in order to compare degree of exfoliating into graphene anddispersibility depending on the presence or absence of additives, thefollowing comparisons of three types of (a), (b) and (c) were carriedout.

(a) No additives

(b) a general dispersing agent (zinc stearate)

(c) a compatibilizer (a graft-modified polymer)

With reference to FIG. 17 showing the measurement results, the resultswill be explained. In addition, in FIG. 17, circles refer to resinmaterials using Sample 1 of the comparative example, and squares referto resin materials using Sample 5 of Example 1.

In case (a) where no additive was added, a difference of the tensilestrengths was small.

In case (b) where the dispersing agent was added, it was revealed thatformation of graphene was promoted to a certain degree in the grapheneprecursor of Sample 5.

In case (c) where the compatibilizer was added, it was revealed thatthat formation of graphene was significantly promoted in the grapheneprecursor of Sample 5. This is because it is considered that, besideseffects to disperse graphene, the compatibilizer binds the graphenelayer-bound bodies and the resin, and acts on them such that thegraphene layer-bound bodies are stripped therefrom, when applying shearin that state.

Zinc stearate is explained above as an example of the dispersing agent.However, those suited for compounds may be selected. As examples of thedispersing agent, anionic (anion) surfactants, cationic (cation)surfactants, zwitterionic surfactants, and nonionic surfactants can bementioned. In particular, anion surfactants and nonionic surfactants arepreferable for graphene. Nonionic surfactants are more preferable. Sincenonionic surfactants are surfactants which do not dissociate into ionsand which show hydrophilic properties by hydrogen bonds with water, asobserved in oxyethylene groups, hydroxyl groups, carbohydrate chainssuch as glucoside, and the like, there is a merit that they can be usedin nonpolar solvents, although they do not have a strength ofhydrophilicity as high as ionic surfactants. Further, this is because,by varying chain lengths of their hydrophilic groups, their propertiescan freely be changed from lipophilic properties to hydrophilicproperties. As anionic surfactants, X acid salts (as for the X acid, forexample, cholic acid, and deoxycholic acid), for example, SDC: sodiumdeoxycholate, and phosphate esters, are preferable. Furthermore, asnonionic surfactants, glycerol fatty acid esters, sorbitan fatty acidesters, fatty alcohol ethoxylates, polyoxyethylene alkyl phenyl ether,alkyl glycosides, and the like are preferable.

Example 5

In order to further verify that those obtained when the Rate (3R) is 31%or more are beneficial as graphene precursors, which is described abovein Example 1, an example in which a graphene precursor was kneaded witha resin will be further explained in Example 5. The following explainselastic moduli of resin molded articles in which graphite-based carbonmaterials containing Samples 1 to 7 in Example 1, having Rates (3R)plotted in FIG. 14, were used as precursors.

(1) Using the above-described graphite-based carbon material as aprecursor, 5 wt % of LLDPE (polyethylene: 20201) produced by PrimePolymer Co., Ltd.) and 1 wt % of a dispersant (nonionic surfactant) weremixed in an ion-exchanged water, and the above-described deviceillustrated in FIG. 8 was actuated under the same conditions, wherebygraphene dispersions containing 5 wt % of graphene and graphite-basedcarbon materials were obtained.

(2) 0.6 kg of the graphene dispersion obtained in (1) was immediatelykneaded into a resin of 5.4 kg using a kneader (pressing-type kneaderWDS7-30 produced by Moriyama Co., Ltd.), whereby pellets were produced.The kneading conditions are to be described below. It should be notedthat the mixing ratio between the resin and the dispersion was selectedso that the amount of the graphene and graphite-based carbon materialsmixed therein was eventually 0.5 wt %.

(3) The pellets produced in (2) were formed into a test piece accordingto JIS K7161 1A (length: 165 mm, width: 20 mm, thickness: 4 mm) by aninjection molding machine.

(4) The elastic modulus (Mpa) of the test piece produced in (3) wasmeasured under a condition of a test speed of 500 mm/min according toJIS K7161 by a table-top type precision universal tester produced byShimadzu Corporation (AUTOGRAPH AGS-J).

The kneading conditions were as follows.

Kneading temperature: 135° C.

Rotor rotation speed: 30 rpm

Kneading time: 15 minutes

Pressurization in furnace: applying 0.3 MPa for 10 minutes after start,and depressurizing to atmospheric pressure after the 10 minutes elapsed

Here, the dispersion of the above-described graphene dispersion into aresin is considered as follows. As the melting point of a resin isgenerally 100° C. or higher, water evaporates in atmosphere, but in apressing-type kneader, the inside of a furnace can be pressurized. Inthe inside of the furnace, the boiling point of water is raised so thatthe dispersion is kept in a liquid form, whereby an emulsion of thedispersion and the resin can be obtained. After applying pressure for apredetermined time, the inside is gradually depressurized, which causesthe boiling point of water to decrease, thereby allowing water toevaporate. Here, graphene confined in water are left in the resin. Thiscauses graphene and graphite-based carbon materials to be dispersed at ahigh concentration in the resin.

Further, since the graphene and graphite-based carbon materials tend toprecipitate in the graphene dispersion as time elapses, the graphenedispersion is kneaded into the resin preferably immediately after thegraphene dispersion is obtained.

It should be noted that the following may be used as the means forobtaining the emulsion of the dispersion and the resin, other than thepressing kneader: a chemical thruster; a vortex mixer; a homomixer; ahigh-pressure homogenizer; a hydroshear; a flow jet mixer; a wet jetmill; and an ultrasonic generator.

Further, the following may be used as a solvent for the dispersion,other than water: 2-propanol (IPA); acetone; toluene;N-methylpyrrolidone (NMP); and N,N-dimethyl formamide (DMF).

Table 4 illustrates the relationship between the Rates (3R) of around30% and the elastic moduli of resin molded articles. It should be notedthat Sample 00 in Table 4 is a blank Sample in which no precursor waskneaded, Samples 11 and 12 have Rates (3R) between that of Sample 1 andthat of Sample 2, and Sample 21 has a Rate (3R) between that of Sample 2and that of Sample 3.

TABLE 4 Sample No. 00 1 11 12 2 21 3 4 P3/(P3 + P4) — 23% 25% 28% 31%35% 38% 42% Elastic 175 197 196 199 231 249 263 272 modulus (MPa)(Average in 5 times) Difference — 12.4%   12.0%   13.9%   31.7%  42.1%   50.0%   55.6%   from blank Under-10 — 10% 12% 25% 25% 30% 38%62% layers upon dispersion in NMP (Reference)

FIG. 18 and Table 4 prove that the difference of the elastic moduluswith respect to that of Sample 00 (blank) (increase ratio of the elasticmodulus) is approximately uniform around 10% until the Rate (3R) reaches31%; after the Rate (3R) reaches 31%, the difference sharply increasesto 32%; while the Rate (3R) increases from 31% to 42%, the differencemonotonously increases to 50%; and after the Rate (3R) reaches 42%, thedifference slightly increases and converges to around 60%. In this way,when the Rate (3R) is 31% or more, a resin molded article having anexcellent elastic modulus can be obtained. Further, since the amount ofgraphene and graphite-based carbon materials contained in a resin moldedarticle is 0.5 wt %, which is small, influence on properties that theresin originally possesses is small.

It is considered that this tendency attributes to a sharp increase in athin graphite-based carbon material containing graphene having 10 orless layers in contact with a resin after the Rate (3R) reaches 31%.Here, in Example 5, it is impossible to determine the number of layersof graphene by observation with TEM due to influences of a dispersantused for dispersion in water. Then, only for reference, the reason forthe sharp increase described above is considered based on thedistribution of the numbers of layers of the graphite-based carbonmaterial illustrated in Table 4 upon dispersion in NMP. Sample 12 andSample 2 are compared with each other, and it is found that both of theproportions of graphene (the number of layers are 10 or less) were 25%.On the other hand, as illustrated in FIGS. 19(a) and 19(b), as to Sample2, the proportion of thin ones having less than 15 layers was greater ascompared with Sample 12; in other words, the graphite-based carbonmaterial dispersed as a precursor had a larger surface area, which meansthat the area thereof in contact with the resin sharply increased.

In this way, Example 5 clearly indicates that when the Rate (3R) is 31%or more, a graphite-based carbon material used as a graphene precursortends to be separated into graphene having 10 or less layers and a thingraphite-based carbon material.

Moreover, in above-described examples 1 to 5, the production apparatus Ausing a jet mill and plasma and the production apparatus B using a ballmill and microwaves are described as a production apparatus whichproduces a graphene precursor. When a treatment based on a radiowaveforce such as by microwaves, millimeter waves, plasma, electromagneticinduction heating (IH), and magnetic fields, and a treatment based on aphysical force such as by a ball mill, a jet mill, centrifugal force,and supercriticality are combined for use, a precursor having a highRate (R3) can be obtained. Therefore, such combination of the treatmentsis preferable. Additionally, as long as the radiowave force-basedtreatments and the physical force-based treatments are used incombination, there is no restriction on a specific kind of the radiowaveforce-based treatments or the physical force-based treatments to beapplied. In particular, as exemplified in the production apparatuses Aand B, it is preferable that effects based on the radiowave force andthe physical force are simultaneously exerted. However, the radiowaveforce and the physical force may be alternately exerted at predeterminedintervals. Moreover, as for the radiowave force, different radiowaveforces, such as treatments based on microwaves and plasma, may bealternately exerted, and, in parallel with the treatments, one or moretreatments based on the physical forces may be exerted. Conversely, asfor the physical force, different physical forces, such as treatmentsbased on a jet mill and supercriticality, may be alternately exerted,and, in parallel with the treatments, one or more treatments based onthe radiowave forces may be exerted.

Moreover, in above-described examples, the production apparatus usingmicrowaves and ultrasonic waves is described as a production apparatusfor obtaining a graphene dispersion using a precursor. However, when atreatment based on a radiowave force such as by microwaves, millimeterwaves, plasma, electromagnetic induction heating (IH) and magneticfields, and a treatment based on a physical force such as by ultrasonicwaves, a ball mill, a jet mill, centrifugal force, and supercriticalityare combined, a graphene dispersion having a high graphene concentrationcan be obtained. Therefore, such combination of the treatments ispreferable. In particular, as seen in the production apparatus, it ispreferable that effects based on a radiowave force and a physical forceare simultaneously directed thereto. However, a radiowave force and aphysical force may alternately be directed thereto at predeterminedintervals.

Furthermore, in the above-described examples, graphene dispersions,conductive inks and resin molded articles are described as applicationsusing precursors. However, also, by mixing, as base materials,precursors into composite base materials such as monomers, polymers,other carbon materials, ceramics, woods, cements or metals, graphenecomposite may be obtained. That is, in the present specification, agraphene composite means products encompassing the above-describedgraphene dispersions, conductive inks and resin molded articles.Additionally, a graphene dispersion encompasses paste products with highviscosities.

As examples of liquids or base materials for dispersing precursors, thefollowing materials can be mentioned. Resins includes polyethylene (PE),polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), ABSresins (ABS), acrylic resins (PMMA), polyamide/nylon (PA), polyacetal(POM), polycarbonate (PC), polyethylene terephthalate (PET), cyclicpolyolefins (COP), polyphenylene sulfide (PPS), polytetrafluoroethylene(PTFE), polysulfones (PSF), polyamide-imide (PAI), thermoplasticpolyimide (PI), polyether ether ketone (PEEK), and liquid-crystalpolymers (LCP). In addition, among synthetic resins, as thermosettingresins, thermoplastic resins such as epoxy resins (EP), phenolic resins(PF), melamine resins (MF), polyurethanes (PUR) and unsaturatedpolyester resins (UP) can be mentioned; fibrous nylon, and fibers ofpolyester, acryl, vinylon, polyolefin, polyurethane, rayon or the likecan be mentioned; as elastomers, isoprene rubbers (IR), butadienerubbers (BR), styrene/butadiene rubbers (SBR), chloroprene rubbers (CR),nitrile rubbers (NBR), polyisobutylene rubbers/butyl rubbers (IIR),ethylene propylene rubbers (EPM/EPDM), chlorosulfonated polyethylene(CSM), acrylic rubbers (ACM), epichlorohydrin rubbers (CO/ECO), and thelike can be mentioned; as thermosetting resin-based elastomers, someurethane rubbers (U), silicone rubbers (Q), fluorine-containing rubbers(FKM), and the like can be mentioned; and, as thermoplastic elastomers,elastomers based on styrene, olefin, polyvinyl chloride, urethane, oramide can be mentioned.

Moreover, as mineral oils, lubricating oils, and greases can bementioned, and, as compounded oils for rubbers, paraffin-based mineraloils, naphthenic mineral oil, aromatic mineral oils, and the like can bementioned.

Furthermore, as nonpolar products, hexane, benzene, toluene, chloroform,ethyl acetate, and the like can be mentioned; as polar aprotic products,acetone, N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP),acetonitrile, and the like can be mentioned; and, as polar proticproducts, acetic acid, ethanol, methanol, water, 1-butanol, 2-propanol,formic acid, and the like can be mentioned.

In addition, as an example of natural graphite for producing agraphite-based carbon material useful as a graphene precursor, particlesof 5 mm or less of a natural graphite material (flaky graphite ACB-50manufactured by Nippon Graphite Industries, ltd.) is described above.However, as for the natural graphite, products which are flaky graphite,being pulverized into 5 mm or less, and which have a Rate (3R) of lessthan 25% and an intensity ratio P1/P2 of less than 0.01 are preferable,from a viewpoint that they are easily-available.

INDUSTRIAL APPLICABILITY

The following can be mentioned as products for attemptingfunctionalization according to graphene by adding the precursor toobjects.

Additives for polymer materials such as resins, rubbers, or coatings

Additives for heat radiation sheets, conductive sheets, heat radiationtapes, or conductive tapes

Sintered metallurgy obtained by adding the precursor to metal powder,followed by sintering

Additives for ceramics such as lithium oxide or nanoclay

Additives for nonmetals such as concrete, or non-polymer materials

The following can be mentioned as products using graphene dispersions.

Electrode agents, conductive auxiliaries, discharge capacity-improvingagents, charge/discharge efficiency-improving agents for lithium-ionbatteries

Electrodes or electrolyte solutions for capacitor products

Conductive agents for conductive inks

REFERENCE SIGNS LIST

-   1 a natural graphite material-   4 a jet mill-   7 a plasma generator-   16 a graphite-based carbon material useful as a graphene precursor-   20 a ball mill-   21 a microwave generator-   24 a media-   25 a natural graphite material-   28 a graphite-based carbon material useful as a graphene precursor-   30 a graphene dispersion using Sample 5-   31 a graphene dispersion using Sample 1-   33 a flake-   40 a beaker-   41 a graphene dispersion-   43 a microwave generator-   44 an ultrasonic wave generator

The invention claimed is:
 1. A graphene composite comprising at least agraphene is partially exfoliated from a graphite-based carbon materialand dispersed in a base material, the graphite-based carbon materialhaving, just before exfoliation of the graphene from the graphite-basedcarbon material, a rhombohedral graphite layer (3R) and a hexagonalgraphite layer (2H), wherein a Rate (3R) of the rhombohedral graphitelayer (3R) and the hexagonal graphite layer (2H), based on an X-raydiffraction method, which is defined by following Equation 1, is 31% ormore:Rate (3R)=P3/(P3+P4)×100  (Equation 1) wherein P3 is a peak intensity ofa (101) plane of the rhombohedral graphite layer (3R) based on the X-raydiffraction method, and P4 is a peak intensity of a (101) plane of thehexagonal graphite layer (2H) based on the X-ray diffraction method, thegraphene being a crystal of a mean size of 100 nm or more and formed ina flake-like or sheet-like shape having 10 layers or less.
 2. Thegraphene composite according to claim 1, being used as a resin moldedarticle.
 3. The graphene composite according to claim 2, wherein thebase material is a resin and a compatibilizer is dispersed in the basematerial.
 4. The graphene composite according to claim 1, being used asconductive ink.
 5. The graphene composite according to claim 4, whereinthe base material is at least one of a solvent and aconductivity-imparting agent.